Heat recovery system



Feb.- 2'3, 1943.

` N( TITLEsTAD ET Al.

HEAT RECOVERY SYSTEM A l Filed ont. 14, 1940 Num. RQ k.. nauw 392.. Swhkm.,

Pafented Feb. '23,1943

2,312,223 naar n EoovEaY SYSTEM .Nicolay Titlestad, White Plains, N. Y., and Louis N; Allen, Jr., Nu'tley, N. J., assignors to Chemical Construction Corporation, New York, N. Y.,

, a corporation of Delaware ,l

"Application october 14, 1940,5seri'a1'1v0. 361,114(v somme. (onza-176) i This invention relates to an'improved process and apparatus for'the manufacture of sulfuric I acid by the contact process, and particularly to a method and apparatus for recovering waste heat generated in such a process. `A principal object of the invention resides in the recovery of the sensible heat contained in the sulfur trioxide gases leaving the catalytic converter in such a form that it may be usefully applied in the gen'- eration of high pressure steamV in-'a waste heat boiler. In many contact sulfuricv acid plantsparticu- I larly in' those which operate with sulfur as raw` and the water isheated,v and thenpassing all or a portion of the resulting superheated water material, it is now standard practice to pass the.

gases from the sulfur"burner throu'gh a` wasteI heat boiler in orderto generate steam from the excess heat contained in these gases. When a boiler is used such as-thatudescribed in U. S.

Patent No. 2,122,390, stack temperatures as low asv550-600 F. can-'be obtained with correspondingly high eiiliciency.l Upon passage of the result 'ing gases through a` catalytic converter after vad.

mixture with additional air if necess'ary,'the resulting sulfur trioxidegases have" a Vtemperature of about 850 F. or higher, depending on the type of converter' employed. It is necessary to cool Y these gases tol much lower temperatures before eillcient absorption can be obtained, and hereto fore this cooling has been carried out in air coolers with no provision for recovering the heat.

The problem of cooling sulfur trioxide gases is much more diiiicult than that of cooling the I .corresponding sulfur dioxide gases of similar moisturecontent. I Any cooling surface in'contact with such gases willv be covered witha nlm of sulfuric acid whenever it has a temperature below the dew pointcf the gases, and corrosion is therefore a serious factor.v 1When it is considered that an effective sulfur trioxide cooler should cool the gasesfor absorption to temperatures of 'about 400"v F., or less, it'4 will'lb'e seen that the problem of recovering useful. heat from this source without excessive corrosion of the equipment is not an easy one.

` vWe have now devised a method and apparatus whereby the excess heatgenerated in the cataf lytic converter of a contact sulfuric acid plant can be recovered as steam while cooling the sulfur Atrioxide gases to temperatures suitable for absorption. In its broadest-aspects our invention isbased on the steps of passing the hots'ulfur trioxide' gases through agas cooler or economizer in heat lexchange relation with a confined body `of water maintained undena relatively high hy drostatic pressure, whereby the gases are cooled into an ordinary waste heat boiler 'of the type referred to aboveA where itssensible heatl is use.

lfully employed in the manufactureofhigh pressure steam. By this means we notonly. recover the excesssensible heat of L the sulfur. trioxide gases..but we ultimately employ this heat energy in the generation ofjhigh pressure steam.`l

The principles of our'iinvention will be described in gre'atcndetail with-referencetothe accompanying drawing, which is a flow sheet# illustrating a preferredfmcdiflation thereof. It

jshouldbe understood, however,y that in manyrespects thisvdrawing is diagrammatic in character; thus, for example, the relative .size-of the economizer or sulfur trioxide gas cooler has been greatly exaggerated in order thatl its 'details-may be shown.

tems may be employed `Within the' scope of the invention.

On the drawing the reference numeral] represents a sulfur burner of a standard type consisting of an elongated chamber 2 provided at one lmedia in the air nlter 9.

end with'an injector type burner 3 having `a central spray nozzle 4 for injecting molten sulfur. from a sulfur melting pit 5 and an outer air in- 4jecting nozzle 6'for surroundingthe stream lof sulfur dropletswith an envelope 'of air from I 'the blower 1. This'air is preferably dried to a.

moisture content of about 0.001-0.003g. per cubic fooifby scrubbing with strong sulfuric acidVV in the. air drier afterwhich it is iltered through sand,` coke, glass Vwool or other suitableiiltering The end of the sulfurburner I opposite the Avsulfur injector 3 is provided witha series of stag'- gered baflles Il forming therewith a combustion chamber to insure complete combustion of thel sulfur.v Inv normal operation .the'gases leaving this chamber have a sulfur/dioxide content of about 13% and a temperature o fv 2000F .2"an d these gases are -passed throughl the pipe I2 into the-gas `inlet of a waste heatboiler Il; iThis boiler is'described in .detail in the patent jof J.

' Ek1und,'No. 2,122,390, dated January 2s, 193s, ano

the description need not ber repeated here. vForV present. purposes `it is sunicient to'state that the boiler is a water tube boiler designed especially for recovering the waste heatpresent in gases,

that it has a gas inlet I2, a stack gas outlet' I4,v a feed water inlet I5 and 'a valved steam outlet.

I t should also be understood that.

.the invention in its broader aspects is notlimited to'the type of plant shown, and that other types of sulfur burners, converters, and absorbing sys- .cipal features .of the present invention.

tion with the .gases nearer its gas exit.

sufficient air in the sulfur burner to insure complete combustion of all the sulfur. Air is usually mixed with the stack gases leavingthe boiler to reduce the sulfur dioxide content to about 7-8%,

and this practice is'illustrated on the drawing wherein additional air from the blower 'l is introduced throughbthe pipe I'I and mixed with the sulfur dioxide gases from the boiler in the pipe I8. `The gas mixture, which then has a temperature of about 43o-450 F., is thereupon introduced into acatalytic converter I 9 of the heat exchange type where its sulfur dioxide content is oxidized to sulfur trioxide inthe presence of a contact masscontaining a catalyst which is preferably an oxide of vanadium.

The converter I3 isillustrated as an internally cooled converter, although itis evident that converters of other types may be used if desired. This-converte'nwhichis now in wide commercial use, contains a lower set of double counter :urrent heat exchangers ,20 which operate'to cool the vlower layer of contact mass` 2I by transferring excess `heat of conversion to the incoming reaction gas mixture and an upper set of heat exchange tubes 22 which vcool theupper catalyst layer 23 by means of air injected through the blower 24. The course of the catalytic reaction is thereby closely controlled, and a 96-98%` conversion of sulfur dioxide to sulfur trioxide is obtained when a highly active vanadium catalyst mass is used. The resultingy sulfur trioxide gases then leave` the converter through the exit pipe` staggered baiilesy 32 and 33 to extend the length of travel of thegases and theupper and lower tube banks 21 and '2t-referred to above. These banks of .tubes are preferably constructed in the form of pipe coils, if a cylindrical economizer-'is used, or in the form of straight lengths connected by joints if the "apparatus is rectangular. In either.` case, however, itis an advantage of the invention that ordinarypiping may be used so that repairs and replacements are greatly simpliv.As is apparent from the drawing the lower tube bank 28 constitutes the main heat exchanging .surface of the economizer and the water therein passes in a direction countercurrent to that of the gases entering through the pipe 25. The upper tube bank 2l -is relatively small in size, and the water therein passes in a direction cocurrent with that of the gases. This arrangement is best suited to avoid condensation of sulfuric acid mist and subsequent corrosion .problems-for the following reasons: 'r 1 Condensation of sulfuric acid from a gas of any given sulfur trioxide and moisture content is a 25 at a temperature of' about 840 F. and are ready for introduction into the economizer or sulfur trioxider cooler which constitutes one of the prin- As has been explained, it is necessary to cool the sulfur trioxide gases from their conversion temperature to about V400 F. in order to obtain han eillcient absorption and conversion of their sulfur trioxide content intostrong sulfuric acid. For this purpose we provide a gas cooler or economizer 26 in the form ofa heat exchanger which is preferably provided with an upper water.

tube bank 2l for passing a stream of water in indirect heat exchange relation with the gases near the tube -banks 2l and 28 of the economizer are always under the samev pressure.

its gas entrance `and a lower tube bank 23 for passing water in indirect heat exchanging relatwo banks of tubes are connected by a pipe 2 9 These so that inoperation` there is a continuous passage of water through thecooler in indirect heatexchanging relation with a continuous stream of the hot sulfur dioxide gases entering through the pipe Nandleaving through the gas exit pipe 3l.

. The economizer 23 illustrated in the drawing is simple in construction and can readily be made Vat relatively low cost from acid-proof materials if desired. However, as will -be explained, the

preferred modifications of the invention operate in such a mannerthat in ordinary operationy the cooler is not subjectfto'sulfuric acid condensation, and in actual practice acid-proof material is not ,usually necessary. The economizer consists essentialhr of an outer shell 3| provided with direct function of the temperature of a condensing surface. In the upper tube bank 21 the outer surfaces of the tubes will have a temperature-between the water temperature and the gas temperature. With4 watertemperatures ofA 20C-250 F. and a gas temperature of about 840- F., as

shown on the drawing, the calculated 'surface temperature isabout300 F., which is suiliciently high to offset corrosion dimculties. l In the lower tube bank 28'the water temperature -is higher (Z50-440 FQ) but ,the gas temperatures are con-l siderably .lower and the surface temperature of the tube remains approximately the same. It will 4 thus be seen that by rst passing the cooler water in heat exchanging relation withthe hot sulfur trioxide gases ventering the cooler and then pass- -ing the resultingr preheated water in countercurrent heat exchange with the same gases nearer the gas exit of the cooler'a relativelyconstant temperature is maintained on the outer surfaces of the cooling coils.

. It is an important feature of the invention that directly connected with the` feed water inlet pipe I5 of lthe boiler by means of a pipe 36 and that the water inlet pipe `35 connects these coils with- ,the boiler feed pump .46. 'Ihe result of this arrangement is that the water in the tube banks 21 and 23 is always under the same hydrostatic pressure as'the water in the boiler so that the steam generated throughout the entire system is With this arrangement the economizer can-be either of the steaming or nonsteaming type, depending upon A the amount of heat to be extractedfrom the sulfur trioxidegases, but in either case the resulting steam or superheated water or mixture thereof is introduced directly into the boiler.

Thisresults inthe addition of all the heat recov-l ered from the sulfur trioxide gases to the heat takenupin the'waste heat boiler I3 and greatly simplifies and cheapens the construction -of the equipment and its ease of operation. A

In addition'to supplying important amounts of v heat to the boiler the superheated water 4in the pipe33 can also be used to preheat the feed water entering through the pipe 35, thereby` overcoming the corrosion problem in the economizer 28 as has been described. Thus, for example, a part of the water from the pipe 36 may be introduced through the 'pipe 3l into a bailled mixing chamber 38 where it is mixed with'feed water entering through the I pipe 39. In ordinary operationsufiicient hot Waterfrom the pipe 36 is prefer-y ably used in this manner to raise the temperature of the feedwater to about 200/ F. or higher, and the mixing` chamber y38 is connected with the Water inletY pipe 35 through the pump 46 so that the feedwater enters the economizer at 4this temperature. Of course; it is equally feasible to employ indirect heat exchange instead of direct heatpexhange'n the feed water heater 38 in means including a catalytic converter for oxidiz- Which'case all the watrin pipe 36 would simply pass through a coil in the feed water heater 38 before being .admitted tothe boiler I3.

The sulfur trioxide gases leaving the economizer through the pipe 30 are admitted to absorbers 40 and 4I which operate in the usualmanner to extract their sulfur dioxide'content by contact with recirculating streams of 98% sulfuric acid. Diluted acid from the drying tower 8 is preferably added to the absorbing system through the pipe ing to sulfur trioxide the sulfur dioxideY content of the gases leaving said" boiler and thereby generating additional heat, a gas cooler having means for passing thehot sulfur trioxide gases Itherethrough, means in said cooler for passing a stream of Water first in concurrent heat exchanging relation with the gases near its gas entrance and then in countercurrent heatexchange rela.

tion with the gases nearer its gas exit, and means for conducting the resulting'heated water from the water outlet of said cooler to the feed water inlet of the Waste heat boiler. I

42 and additional Water may be introduced through the pipe 43 if Inecessary. Inasmuch as the greater part of the heat has been removed from the entering sulfur trioxide gases bythe operation of the economizer 2B, no excess burden is placed on the acid cooling coils ,44 and 45 and a thorough and efcient heat recovery is obtained in the entire plant.

' What we claim is:

1. Apparatus for recovering waste heat generated in a contact sulfuric acid process comprising in combination a Waste heat boiler and means for passing hot sulfur dioxide gases therethrough, means including a catalytic converte:

content of the gases leaving said boiler and thereby generating additional heat, a gas cooler havingl a water inlet and a water outlet, means for passing hot sulfur trioxide gases from the converter through said gas cooler, means for 3. Apparatus for recovering waste heat generated in a contact sulfuric acid process comprising in combination a waste heat boiler and means for passing hot sulfur dioxide gases therethrough, ,means including a catalytic converter for oxidizing to sulfur trioxide the sulfur dioxide content of the gases leaving vsaid boiler and thereby generating additional heat, a gas cooler having means for passing the hot sulfur trioxide gases therethrough, means in saidl cooler for passing a stream of water first in indirect heat exchanging relation with the gases near its gas entrance and then with the gases nearer its gas exit, means for conducting the resulting heated water from the water outlet of said cooler to the feed Water inlet of the waste heat boiler, and

means for preheating feed water for said cooler -by heat exchange with the hot Water leaving said cooler, whereby excessive chilling of' the sulfur lforoxidizing to. sulfur trioxide the sulfur dioxide trioxide gases is avoided. 4. A method of recovering waste heat gener ated in a contact sulfuric acid process which comprises the steps of first passing hot sulfur dioxide gases in heat exchanging relation with a confined body of water to remove excess heat passingwater throughV said cooler in indirect.' l

'heat exchanging. relation with said gases to extract heat therefrom, means for conducting the resulting heated water from the Water outlet of lsaid cooler to the feedwater inlet of the wasteheat boiler, and means for'preheating'feed water for said cooler by heat' exchange with water leaving said cooler whereby excessive chilling of the sulfur trioxide gases is avoided. y

2. Apparatus for recovering waste heat generated in a contact sulfuric'acid process comprising in combination a waste heat boiler and means for passing hot-sulfur dioxide gases therethrough,

therefromand generate steam under pressure, then oxidizing to sulfur trioxide the sulfur dioxide content of the gases and 'thereby' generating additional heat, then passing the resulting hot sulfur trioxide gases inheat exchanging relation with a second confined body`of water preheated in the manner hereinafter described and maintained under a pressure substantiallyequal to that of said first confined body of water to fur-- ther heat said water and aid in theV generation of steam, and then transferring heat from the resulting heated water to cold feed water for the system in orden to preheat said cold feed water.

, NIcoLAY 'n'rLEsTAn Lours N. ALIEN, Jn. 

